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第891 14609號專利申請案 中文說明書修正頁(91年3月） 五 發明説明（1 ) 本發明係關於一種製備二氧化錘纖維之方法。本發明更 關於一種製備安定二氧化锆纖維之方法，其中藉安定添加 劑安定二氧化錘之四面體修改體以避免轉變成為單斜晶修 改體。 由於其性質，在需要材料之高機械、熱與化學抗性之應 用領域以增加之程度使用二氧化錯。例如，二氧化錘可單 獨或混合其他氧化物作為用於製備燒結陶瓷之成形體或纖 維之材料。例如，二氧化锆纖維用於特定之絕熱應用中。 其他之應用領域為金屬之纖維強化以增加其強度及潛變抗 性。其特別地應用於纖維強化鈦與鈦合金，因為鈦在特定 條件下反應在其他金屬之情形中使用之氧化鋁纖維。此 外，二氧化锆纖維在高溫（例如，高於800°C )為良好之氧離 子傳導體，而且因此用於如感應器或燃料管之適合組件。 此外，；氧化锆纖維對強鹼與氯為惰性，如此使其可在用 於氯鹼電解質之膜片中取代石綿。 用於這些燒結體或纖維之二氧化錘粉末通常以安定形式 使用，結果，即使在冷卻至使用溫度之後亦保留四面體高 溫修改體。為了完成此種安定，以其他之氧化物摻染二氧 化錘粉末，如氧化釔、氧化鈽、稀土族之氧化物、氧化 鈣、氧化鎂或這些氧化物之混合物。為了尋求使由安定二 氧化锆製備之胚體，例如，藉由壓製、注射成型、滑鑄或 纺絲，具有所需之燒結行為，及使燒結成形體或纖維具有 良好之機械、熱與化學性質，摻染物氧化物儘可能地均勻 分布於二氧化結晶格内為必要的。 -4- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 495569 A7 _B7_ 五、發明說明（2 ) 製備未安定或安定二氧化锆纖維之方法為已知的。 例如，依照US-A 3944640專利，自二氧化锆熔化體抽取 二氧化锆纖維。由於其高能量成本，此方法在經濟上不令 人滿意。T. Yogo 在 J. Mater. Sci. 25(5)(1990)2394-2398 及 Y. Abe、H. Tomioka、T. Gunji、Y. Nagao 與 T. Misono在 J. Mater. Sci. Lett. 13(13)(1994)960-962教示其中將聚合有機锆化合物 成形以形成纖維，繼而藉熱解轉化成為二氧化錯纖維之方 法。此方法在經濟上亦不令人滿意，因為經有機锆化合物 之路徑為複雜的。 在其他之已知方法中，例如，揭示於DE-A 30 28 3 14專利 者，處理粉碎二氧化锆以形成纖維。因此，將具有0.1至1 微米粒度之安定或未定定二氧化锆顆粒分散於輔助聚合物 或其溶液中，並且經細噴嘴擠製得到之黏性混合物。繼而藉 缓慢加熱去除溶劑，燃燒聚合物且藉由在1300°C至1500°C燒 結而製備最終之纖維。這些方法通常造成相當脆之纖維。 經濟部智慧財產局員工消費合作社印製 L裝。-- (請先閱讀背面之注意事項再填寫本頁) 其他之方法，例如，揭示於EP-A 375 158與EP-A 383 051 專利者，由二氧化锆溶膠開始，其通常藉烷氧化锆化合物 之水解製備。將溶膠纺絲且藉燃燒製備最終之纖維。使用 烷氧化锆化合物作為起始材料使這些方法在經濟上不令人 滿意。 其他之已知方法由溶解之二氧化锆化合物開始，將溶液 成形以形成纖維，繼而藉烺燒將其轉化成二氧化锆。此種 方法之實例揭示於 JP-A 04-100 921、JP-A 02-097 425 或 JP-A 05-321 036專利。由溶解之二氧化锆化合物開始之所有已 本紙張尺度適用中國國家標準（CNS〉A4規格（210 X 297公釐） A7 A7 五 經濟部智慧財產局員工消費合作社印制衣 發明說明（ 知方法均需要小心地控制方法條件，因爲即使是小誤差亦 造成不令人滿意之結果。特別地，應避免固體顆粒之早熟 形成’因爲其在未來之纖維中表現爲破碎來源。許多此種 方法之其他缺點爲其由含氯化物二氧化锆開始。存在於最 終纖維中之氣化物可永久地損害其性質，而且在一些應用 中亦造成腐蝕問題。 JP-A 61-289130專利敎示一種藉由將含基於溶液之總鹽含 I爲5至30重量％之乙酸锆之曱酸锆溶液紡絲，繼而燒結 而製備士足二氧化锆纖維之方法。如果在此方法中使用較 少之乙酸锆，則無法得到可紡絲溶液，而如果使用太多， 得到之纖維強度降低。 DE-A 196 19 638專利揭示一種由無氯锆化合物在甲酸/水 混合物中之溶液製造安定或未安定二氧化锆粉末之方法。 本發明I目的爲發現更簡單且在經濟上令人滿意之製備 二氧化锆纖維之方法，而可製造高品質之安定或未安定纖 維。 已發見此目的藉由將錐化合物之溶液紡絲繼而懷燒而製 備二氧化锆纖維之方法完成，其中使用锆化合物在甲酸/ 水混合物中之溶液。 ，，二之方法可以簡單及經濟之方式製備具有優良性質 Γ7抑貝安疋或未安疋一氧化锆纖維。亦可不使用含氣起 始材料而製備纖維。 (請先閱讀背面之注意事項再填寫本頁) 裝 在本發明方法之第-步驟中，製備锆化合物在曱酸/水 混合物中之可纺絲溶液。因此，锆化合物，較佳爲無氣結Patent Application No. 891 14609 Revised Chinese Manual (March 91) V. Description of the Invention (1) The present invention relates to a method for preparing hammer dioxide fibers. The present invention further relates to a method for preparing a stabilized zirconia fiber, in which a tetrahedral modification of a stable dioxin hammer is stabilized by a stabilizer additive to avoid transformation into a monoclinic modification. Due to its nature, dioxide is used to an increased extent in applications that require high mechanical, thermal and chemical resistance of the material. For example, the hammer may be used alone or in combination with other oxides as a material for forming a shaped body or fiber for sintered ceramics. For example, zirconia fibers are used in specific thermal insulation applications. Other applications are metal fiber reinforcement to increase its strength and creep resistance. It is particularly applied to fiber-reinforced titanium and titanium alloys because titanium reacts with alumina fibers used in the case of other metals under specific conditions. In addition, zirconia fibers are good oxygen ion conductors at high temperatures (e.g., above 800 ° C) and are therefore used in suitable components such as inductors or fuel pipes. In addition, zirconia fibers are inert to strong alkalis and chlorine, which makes it possible to replace asbestos in membranes used in chlor-alkali electrolytes. Hammer dioxide powder for these sintered bodies or fibers is usually used in a stable form, and as a result, the tetrahedral high-temperature modified body is retained even after cooling to the use temperature. To accomplish this stabilization, hammer oxide powder is doped with other oxides, such as yttrium oxide, hafnium oxide, rare earth oxides, calcium oxide, magnesium oxide, or mixtures of these oxides. In order to seek to make embryonic bodies made of stable zirconia, for example, by pressing, injection molding, slip casting or spinning, to have the desired sintering behavior, and to make the sintered shaped bodies or fibers have good mechanical, thermal and chemical properties By nature, it is necessary for the dopant oxide to be distributed as uniformly as possible in the crystal lattice of the dioxide. -4- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 495569 A7 _B7_ V. Description of the invention (2) The method for preparing unstabilized or stabilized zirconia fibers is known. For example, according to US-A 3944640, zirconia fibers are extracted from a zirconia melt. Due to its high energy cost, this method is not economically satisfactory. T. Yogo in J. Mater. Sci. 25 (5) (1990) 2394-2398 and Y. Abe, H. Tomioka, T. Gunji, Y. Nagao, and T. Misono in J. Mater. Sci. Lett. 13 (13) (1994) 960-962 teaches a method in which a polymeric organic zirconium compound is shaped to form a fiber, which is then converted into a dioxide fiber by pyrolysis. This method is also economically unsatisfactory because the path through the organic zirconium compound is complicated. Among other known methods, for example, disclosed in the patent of DE-A 30 28 3 14 is the treatment of pulverized zirconia to form fibers. Therefore, stable or undetermined zirconia particles having a particle size of 0.1 to 1 micrometer are dispersed in an auxiliary polymer or a solution thereof, and the obtained viscous mixture is extruded through a fine nozzle. The solvent is then removed by slow heating, the polymer is burned and the final fiber is prepared by sintering at 1300 ° C to 1500 ° C. These methods often result in fairly brittle fibers. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. -(Please read the notes on the back before filling this page) Other methods, for example, disclosed in EP-A 375 158 and EP-A 383 051. The patentees start with zirconium dioxide sol, which usually borrows zirconia alkoxide Preparation of compounds by hydrolysis. The sol is spun and the final fiber is prepared by combustion. The use of zirconium alkoxide compounds as starting materials makes these processes economically unsatisfactory. Other known methods start with a dissolved zirconia compound, shape the solution to form fibers, and then convert it to zirconia by calcination. Examples of such a method are disclosed in JP-A 04-100 921, JP-A 02-097 425, or JP-A 05-321 036. All the paper sizes starting from the dissolved zirconia compounds are in accordance with Chinese national standards (CNS> A4 specifications (210 X 297 mm) A7 A7 Five of the Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed Garment Invention Description The process conditions need to be carefully controlled, as even small errors can cause unsatisfactory results. In particular, the premature formation of solid particles should be avoided 'because they appear to be a source of fragmentation in future fibers. Many of these other methods The disadvantage is that it starts with zirconium dioxide containing chloride. The gaseous substances present in the final fiber can permanently impair its properties and also cause corrosion problems in some applications. The JP-A 61-289130 patent shows a method by which A method for preparing a zirconia fiber with fibrous zirconia by spinning a solution of zirconium acetate containing 5 to 30% by weight of zirconium acetate based on the total salt content of the solution. If less zirconium acetate is used in this method, It is impossible to obtain a spinnable solution, and if too much is used, the strength of the obtained fiber is reduced. The DE-A 196 19 638 patent discloses a kind of Method for producing stable or unstabilized zirconia powder from a solution in an acid / water mixture. The object of the present invention is to find a simpler and economically satisfactory method for preparing zirconia fibers, which can produce high-quality stability Or unstabilized fibers. It has been found that this purpose is accomplished by spinning a solution of a cone compound followed by calcination to prepare zirconia fibers, which uses a solution of a zirconium compound in a formic acid / water mixture. Simple and economical methods can be used to prepare Γ7 Imbiram or non-ammonia zirconia fibers with excellent properties. Fibers can also be prepared without using gaseous starting materials. (Please read the precautions on the back before filling this page) In the first step of the method of the present invention, a spinnable solution of a zirconium compound in an osmic acid / water mixture is prepared. Therefore, the zirconium compound is preferably airless.
495569 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（4 化合物，溶於甲酸/水混合物中。使用之锆化合物爲，例 如，氧化锆水合物或鹼性碳酸锆。在此溶劑中，甲酸對水 之莫耳比例爲1:1至1:3，較佳爲1:1 5至1:2 5，而且非常 特佳爲1 : 1.8至2.2。甲酸/水混合物較佳爲不含其他成分。 溶劑可在室溫或稍高之溫度製備，但是較佳爲使用5〇至95。〇 之範圍，更佳爲70至85°C之範圍之溶解溫度。通常，將甲 酸與水之混合物置於溶解容器中且加入固體，但是同樣地 可爲相反之順序。在使用碳酸鹽時，加成速率較佳爲設定 爲使得恰好防止反應器之内容物起泡。 原則上藉由，例如，將1公斤之鹼性碳酸鍺溶於〇 4公斤 之水與0.5公斤之甲酸之混合物中，可得到低黏度透明溶液 。藉由將1公斤之鹼性碳酸錘溶於僅〇 24公斤之水與〇 公斤I甲酸之混合物中，同樣地可製備高黏度之同樣透明 溶液。爲了得到最適之纺絲力，冑由蒸發溶劑以濃縮低黏 度溶液或以其他之溶劑加入高黏度溶液。爲了儘可能地節 省額外之方法步驟，較佳爲锆化合物溶於大約其本身重量 之甲酸/水混合物中。 如果需要，本發明之方法亦可製備安定二氧化锆纖維。 因此，在其製備之前、之時或之後，將安定四面體修改體 以避免轉變成爲單斜晶修改體之添加劑加入二氧化錯。例 如，此種化合物之安定化合物或先質，其有利地同樣溶於 甲酸/水混合物中，可如固體混合至用於本發明方法之锆 化合物中（在其溶於曱酸/水混合物中之前）。同樣地，例 如，在已藉由沈澱水合氧化物、碳酸鹽、草酸鹽或類似化 -裝--- (請先閱讀背面之注意事項再填寫本頁) ·495569 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (4 compounds, soluble in formic acid / water mixture. The zirconium compounds used are, for example, zirconia hydrate or alkaline zirconium carbonate. In this solvent In the formula, the molar ratio of formic acid to water is 1: 1 to 1: 3, preferably 1: 1 to 1:25, and very particularly preferably 1: 1.8 to 2.2. The formic acid / water mixture is preferably not Contains other ingredients. The solvent can be prepared at room temperature or slightly higher, but it is preferred to use a dissolution temperature in the range of 50 to 95 °, more preferably 70 to 85 ° C. Generally, formic acid and water are used. The mixture is placed in a dissolution vessel and solids are added, but the reverse order is equally possible. When carbonates are used, the addition rate is preferably set such that foaming of the reactor contents is just prevented. In principle, For example, by dissolving 1 kg of basic germanium carbonate in a mixture of 0.4 kg of water and 0.5 kg of formic acid, a low-viscosity transparent solution can be obtained. In a mixture of water and 0 kg of I formic acid, the same The same transparent solution with high viscosity can be prepared. In order to obtain the optimal spinning force, the solvent is evaporated to concentrate the low viscosity solution or other solvents are added to the high viscosity solution. In order to save extra method steps as much as possible, zirconium is preferred The compound is dissolved in a formic acid / water mixture of about its own weight. The method of the present invention can also prepare stable zirconium dioxide fibers if necessary. Therefore, before, during, or after its preparation, the stable tetrahedral modification is avoided Additives that are converted into monoclinic modification are added to dioxo. For example, stable compounds or precursors of such compounds, which are likewise advantageously soluble in formic acid / water mixtures, can be mixed as solids into the zirconium used in the method of the invention Compound (before it is dissolved in the osmic acid / water mixture). Similarly, for example, after having precipitated hydrated oxides, carbonates, oxalates or similar (Please fill out this page again)
495569 第891 14609號專利申請案 中文說明書修正頁(91年3月） 發明説明（ 合物之开;；式之安定氧化物先質 、 几貝向I備义後，可將安定添加 劑或此種添加劑之先質引人松 ' 』无貝？丨入依照本發明製備之二氧化錘纖 維中’此類似化合物可藉由在懸浮液中馈燒纖維，去除懸 洋足揮發性組份’及懷燒而轉化成為氧化物。，然而，較佳 為在甲酸與水混合物中將至少—種安m劑及/或此種添 加劑之至少一種先質與錯化合物—起溶解。較佳為使用纪 化合物作為安定添加劑或先質。較佳為使用溶於作為溶劑 之甲酸與水混合物中之無氯釔化合物。適合之含釔化合物 為，例如，氧化釔及碳酸釔。通常，計算釔化合物之量使 得二氧化锆纖維具有2至1〇莫耳％，較佳為2 5至5莫耳％之 氧化釔含量。在製備安定二氧化鍺纖維時，溶解之化合物 總量較佳為溶於大約其本身重量之甲酸/水混合物中。 在已製備溶液之後，將其攪拌或靜置直到其完全透明或 在冷卻至低於30°C之後完全透明。通常，其為在室溫靜置 最多20小時之情形。如果在高溫製備溶液，應注意雖然較 快速地製備溶液，其通常在高於3(rc為混濁的。 繼而調整溶液之黏度使得其為可紡絲的。因此，蒸發溶 刻（較佳為在主溫藉低於大氣壓力）或加入溶劑。在室溫及 10秒-1之切力速率之黏度較佳為2000至10,000 dpas之範圍。其 以氧化物（Zr〇2，如果可應用，或為Zr〇2 /安定劑，例如， Y2 〇3)汁鼻’對應40至50重里％纺絲組合物之固體含量。 繼而藉習用纺絲技術將可纺絲溶液纺絲以形成纖維。# 絲步驟可在空氣中及在室溫進行。製備之纖維通常具有5 至2 0微米之直徑，而且以達1米/秒之速度直接由溶液柚取 -8- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐） 第891 14609號專利申請案 中文說明書修正頁(91年3月） R7495569 Patent Application No. 891 14609 Revised Chinese Specification Sheet (March 91) Description of the Invention (Composition of the compound; the stable oxide precursor of the formula, the chirped beetle can be prepared to I, then the stabilizer additive or such The precursor of the additive is attractive "" No shellfish? "Into the hammer dioxide fiber prepared according to the present invention," This similar compound can be removed by burning the fiber in the suspension to remove the volatile components of the suspension foot "and It is converted into an oxide by burning. However, it is preferred to dissolve at least one of the ammonium agent and / or at least one of the precursor and the wrong compound of such an additive in a mixture of formic acid and water. The use compound is preferred As a stabilizer additive or precursor. It is preferred to use yttrium-free compounds dissolved in a mixture of formic acid and water as a solvent. Suitable yttrium-containing compounds are, for example, yttrium oxide and yttrium carbonate. Generally, the amount of yttrium compound is calculated such that Zirconium dioxide fibers have an yttrium oxide content of 2 to 10 mole%, preferably 25 to 5 mole%. When preparing stable germanium dioxide fibers, the total amount of dissolved compounds is preferably soluble in about itself weight In a formic acid / water mixture. After the solution has been prepared, it is stirred or left to stand until it is completely transparent or after cooling to below 30 ° C. Generally, it is left to stand at room temperature for a maximum of 20 hours. Situation. If the solution is prepared at high temperature, it should be noted that although the solution is prepared more quickly, it is usually higher than 3 (rc is turbid. Then adjust the viscosity of the solution so that it is spinnable. Therefore, evaporation and melting (better To reduce the atmospheric temperature at the main temperature) or add a solvent. The viscosity at room temperature and a shear rate of 10 seconds -1 is preferably in the range of 2000 to 10,000 dpas. It is based on oxides (ZrO2, if applicable) Or ZrO2 / stabilizer, for example, Y2O3) juice nose 'corresponds to a solid content of 40 to 50% by weight of the spinning composition. Then spin spinning the spinnable solution to form fibers. # The silk step can be performed in the air and at room temperature. The prepared fibers usually have a diameter of 5 to 20 microns, and can be directly taken from the solution grapefruit at a speed of up to 1 m / s. -8- This paper size applies to Chinese national standards (CNS) A4 size (210 X 297 mm) No. 891 14 Chinese Patent Application No. 609 Revised Chinese Manual (March 91) R7
五、發明説明（e ) ' ---—~ ’或在纺絲步驟後以達10米/秒之速度抽取，以產生2至1〇 微米範圍之直徑之纖維。由於其高固體含量，以此方式製 造之”胚料”纖維非常快速地乾燥而形成不黏在一起之非晶 形似玻璃纖維。 胚料二氧化锆纖維成為最終產物之轉化為已知的。如果 需要，藉由將胚料纖維曝露於至少10(TC之溫度而自其去除 仍存在於胚料纖維中之甲酸及/或水C，乾燥”）；低於300。〇之 溫度通常對其為足夠的。繼而以習用方式藉由在不低於600 C j：段燒胚料纖維（如果需要，在乾燥後）而製備最終二氧化 锆纖維。如果達到這些溫度之加熱速率低於習用者，可使 用之溫度範圍變為稍低，而在此習用高之加熱速率之情 形，其變為較高。為了工業製備連續纖維，較佳為在加熱 軸之下端進行紡絲，其具有至多1〇米之長度，而且加熱 至，例如，1500°C。在纖維離開紡錘後直接發生抽取。以 此方式，在軸之上端得到最終之連續二氧化锆纖維。短纖 維較佳為以離心法藉由經具有紡錘位於其周圍之轉動冷卻 纺絲頭塵製溶液而製備。頭位於加熱至12〇〇至1500°C之爐 中。此方法產生具有至多2毫米長度之最終短二氧化錘纖維。 實例 將1000克之鹼性碳酸锆（計算之二氧化锆含量：44重量％) 及25克之氧化釔置於開放塑膠容器中。在室溫加入1000克 之561克甲酸與439克水之混合物而生成二氧化碳散逸。混 合物在室溫維持20小時而形成透明溶液。此溶液在轉動蒸 發器上濃縮直到可藉玻璃棒自其抽取數米長纖維。基於 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 495569 第891 14609號專利申請案 中文說明書修正頁(91年3月） Α7Π B7 修正 缝·補充1 7 五、發明説明（ 二氧化锆及氧化釔之總和計算，以此方式得到之纺絲組合 物之固體含量為44.2重量％。 在爐中在空氣中將在室溫在空氣中使用玻璃棒人工抽取 之纖維加熱至1450°C，在此溫度靜置10分鐘繼而冷卻。形 成具有5至10微米之直徑之撓性二氧化#纖維。 10- 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐)V. Description of the invention (e) '----- ~' or after the spinning step, it is extracted at a speed of 10 m / s to produce fibers with a diameter in the range of 2 to 10 microns. Due to its high solids content, the "blank" fibers made in this way dry very quickly and form amorphous glass fibers that do not stick together. The conversion of the billet zirconia fibers into the final product is known. If necessary, remove formic acid and / or water C still present in the raw material fibers from the raw material fibers by exposing the raw material fibers to a temperature of at least 10 (TC, dry "); temperatures lower than 300 ° are usually applied to them. It is sufficient. Then, in a conventional manner, the final zirconia fiber is prepared by burning the preform fiber at a temperature of not lower than 600 Cj: (if necessary, after drying). If these temperatures are reached, the heating rate is lower than the conventional one , The usable temperature range becomes slightly lower, and in the case of high heating rates used here, it becomes higher. For the industrial production of continuous fibers, it is preferred to spin at the lower end of the heating shaft, which has a maximum of 1 The length is 0 meters, and it is heated to, for example, 1500 ° C. The extraction takes place directly after the fibers leave the spindle. In this way, the final continuous zirconia fibers are obtained at the upper end of the shaft. The short fibers are preferably borrowed by centrifugation. Prepared by making a solution from a spinning cooled spinning head with a spindle located around it. The head is located in a furnace heated to 12,000 to 1500 ° C. This method produces a final short hammer fiber with a length of up to 2 mm. Example: 1000 g of basic zirconium carbonate (calculated zirconia content: 44% by weight) and 25 g of yttrium oxide are placed in an open plastic container. A mixture of 1,000 g of 561 g of formic acid and 439 g of water is added at room temperature to produce Carbon dioxide dissipates. The mixture is maintained at room temperature for 20 hours to form a transparent solution. This solution is concentrated on a rotary evaporator until a few meters of fiber can be extracted from it by a glass rod. Based on this paper standard, China National Standard (CNS) A4 specification (210 X 297 mm) 495569 Patent Application No. 891 14609 Revised Chinese Manual (March 91) Α7Π B7 Correction seam · Supplement 1 7 V. Description of the invention (calculation of the sum of zirconia and yttrium oxide in this way The spinning composition had a solids content of 44.2% by weight. The fibers artificially extracted with glass rods at room temperature in the air were heated in a furnace to 1450 ° C in the air, left at this temperature for 10 minutes, and then cooled. Formed Flexible Dioxide # fiber with a diameter of 5 to 10 microns. 10- This paper size applies to China National Standard (CNS) A4 (210X 297 mm)